JP2017037296A - Toner composition and process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester-based toner having a low fixed temperature and the wide degree of freedom in fusion, and a toner composition and a process that can manufacture a more economic polyester.SOLUTION: There is provided a toner composition containing an amorphous polyester resin, crystalline polyester resin, colorant, and wax, wherein the amorphous polyester resin is produced through catalyst polymerization of a monomer of a component selected from the group consisting of a carboxylic acid, dicarboxylic acid, benzene tricarboxylic acid, at least one bisphenol, and at least one of anhydride dodecyl succinic acid and dodecyl succinic acid; the amorphous polyester resin contains the component in an amount of approximately 8 to approximately 15.9 weight%.SELECTED DRAWING: None

Description

  The present disclosure relates generally to toner compositions and processes thereof, and more specifically composed of one type of amorphous polyester resin, crystalline polyester, colorant, optional wax, and optional additive, The amorphous polyester resin is made, for example, by catalytic polymerization of a monomer of a component selected from the group consisting of carboxylic acid, dicarboxylic acid, benzenetricarboxylic acid, at least one bisphenol, at least one of dodecyl succinic anhydride and dodecyl succinic acid. The amorphous polyester resin relates to an economical toner containing less than about 16% by weight of dodecyl succinic anhydride.

  Many toner compositions containing polyester are known, including those in which the selected polyester is a particular amorphous, crystalline, or mixture thereof. Thus, for example, US Pat. No. 7,858,285 discloses an emulsified / aggregated toner comprising a specific crystalline polyester.

  Toner compositions prepared by a number of emulsification / aggregation processes where the toner may include certain polyesters are described in US Pat. Nos. 8,466,254; 7,736,832; 7,029,817. No .; 6,830,860 and 5,593,807.

  These known toners may be suitable for their intended purpose, but include, for example, tolerance characteristics and superior characteristics related to fixed temperature freedom and blocking temperature, such as from about 52 ° C. to about There remains a need for toners having a blocking temperature of 60 ° C. There is also a need for a polyester-containing toner having excellent gloss, improved coagulation properties and blocking temperature characteristics, acceptable minimum fixing temperature, excellent hot and cold offset temperatures, and having the desired particle size. . Further, there is a need for a toner composition that does not substantially transfer or set off to the xerographic fuser roller (whether it is below the fixed temperature of the paper (cold offset) or above the fixed temperature of the toner). Depending on whether toner is set off to the fuser roller at temperature (called hot offset or cold offset).

  Furthermore, it can be prepared economically, for example terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate) terpoly- (propoxylated bisphenol A-fumarate). ) (Comparative Example A, Table 1) and terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) terpoly Two types of amorphous polyesters:-(ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate) (Comparative Example B) Instead of ether resin, there is a need for toner present one type of amorphous polyester resin selected.

  In addition, it is composed of one kind of economical amorphous polyester made from the use of a specific amount of dodecyl succinic anhydride (DDSA) monomer, which is fused, solidified (blocking), toner particle size, toner particle shape CPE 10: 6 resin of plasticized or specific polyester (eg, poly (1,6-hexylene-1,12-dodecanoate) to provide excellent tolerance characteristics such as resin glass transition temperature and triboelectric characteristics ), And if desired, containing a small amount of wax component, the CPE 10: 6 resin is poly (1,6-hexylene-1,12-dodecanoate) and the resin There is a need for a toner composition that can be made by the reaction of dodecanedioic acid and 1,6-hexanediol. .

  Furthermore, there is a need for toners and processes that can make economical polyesters.

  An amorphous polyester resin, a crystalline polyester resin, a colorant and a wax core, and an amorphous polyester resin, a wax and a colorant shell thereon, and the core and shell amorphous polyester resin are costly monomers There is also a need for toners that can be made using small amounts of dodecyl succinic anhydride (DDSA).

  Further, there is a need for a polyester-based toner having a low fixing temperature (for example, about 100 ° C. to about 130 ° C.) and a wide degree of fusion freedom (for example, about 50 ° C. to about 90 ° C.).

  Another need provides toners having improved blocking temperatures, such as at least about 52 ° C, such as from about 52 ° C to about 59 ° C, from about 52 ° C to about 55 ° C, and from about 52 ° C to about 55 ° C. There is to do.

  In addition, toners having consistently small particle sizes (eg, average diameter of about 1 to about 15 microns), suitable shapes that save energy, narrow particle size GSD, and various core-shell structures Is needed.

  These needs and advantages, as well as other needs and advantages, can be achieved in some embodiments using the processes and compositions disclosed herein.

  The amorphous polyester resin is composed of an amorphous polyester resin, a crystalline polyester resin, a colorant and a wax, and the amorphous polyester is formed from at least one of carboxylic acid, dicarboxylic acid, benzenetricarboxylic acid, at least one bisphenol, dodecyl succinic anhydride and dodecyl succinic acid. Disclosed is a toner composition made by catalytic polymerization of a monomer of a component selected from the group, wherein the amorphous polyester resin comprises from about 8 to about 15.9% by weight of said component.

  And a core of an amorphous polyester resin, a crystalline polyester, a wax and a colorant, and at least one shell that encloses the core and is composed of an amorphous polyester resin and optionally a wax. Amorphous polyester for is made by catalytic polymerization of carboxylic acid, dicarboxylic acid, benzenetricarboxylic acid, at least one bisphenol and dodecyl succinic anhydride or dodecyl succinic acid monomer, said amorphous polyester resin having a zero percent excess of said Dodecyl succinic anhydride or the amorphous polyester resin contains a zero percent excess of the dodecyl succinic acid and the amorphous polyester is less than 16% by weight of the amorphous polyester resin. Or containing decyl succinic acid, or, the amorphous polyester resin comprises the dodecyl succinic acid of less than 16% by weight, the toner composition is disclosed.

  Further, the present specification includes mixing an amorphous polyester resin, a crystalline polyester resin, a colorant and a wax, and the amorphous polyester includes carboxylic acid, dicarboxylic acid, benzenetricarboxylic acid, at least one bisphenol, dodecyl succinic anhydride, and Made by catalytic polymerization of a monomer of a compound selected from the group consisting of dodecyl succinic acid, wherein the amorphous polyester resin comprises from about 8 to about 15.9% by weight of the compound, agglomerated and fused; A process is shown that includes making toner particles.

  The disclosed amorphous polyester resins generally react with a suitable organic diol and a suitable organic diacid in the presence of a polycondensation catalyst and dodecyl succinic anhydride (DDSA), dodecyl succinic acid or mixtures thereof. Embodiments that include and refer to dodecyl succinic anhydride (DDSA) herein also include dodecyl succinic acid.

  Disclosed herein is a toner composition comprising an amorphous polyester resin, at least one crystalline polyester resin, a colorant, a wax, and optional additives. The toner composition shown herein can be prepared by an emulsification / aggregation / fusion process and is an economical type of amorphous polyester resin, crystalline polyester, such as CPE 10 shown herein: 6. Contains wax, colorant and toner additives.

  In some embodiments, the disclosed toner comprises, for example, one amorphous polyester, crystalline polyester, wax, colorant and additive core and at least one shell thereon, for example, about one type. Shells to about 5 types of shells, more specifically, about 1 type of shells to about 3 types of shells, and more specifically about 1 type of shells to about 2 types of shells. Also good.

(Amorphous polyester)
Many amorphous polyesters available from Kao Corporation, DIC Chemicals, and Reichhold Chemicals may be selected for the toners shown herein. For example, terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate) terpoly- (propoxylated bisphenol A-fumarate) (Comparative Example A) first resin And, for example, terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (ethoxylated bisphenol A-terephthalate) terpoly- (ethoxylated bisphenol A- Selected as a replacement for prior art mixtures of dodecenyl succinate) -terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate) (Comparative Example B) with a second resin. Examples of amorphous polyesters that may be used include poly (propoxylated bisphenol cofumarate), poly (ethoxylated bisphenol cofumarate), poly (butyloxylated bisphenol cofumarate), poly (co-propoxylated bisphenol cofumarate). -Ethoxylated bisphenol cofumarate), poly (1,2-propylene fumarate), poly (propoxylated bisphenol copolymer), poly (ethoxylated bisphenol copolymer), poly (butyloxylated bisphenol copolymer) ), Poly (co-propoxylated bisphenol co-ethoxylated bisphenol co-maleate), poly (1,2-propylene maleate), poly (propoxylated bisphenol co-itaconate), Poly (ethoxylated bisphenol co-itaconate), poly (butyloxylated bisphenol co-itaconate), poly (co-propoxylated bisphenol co-ethoxylated bisphenol co-itaconate), and terpoly (propoxylated bisphenol A-terephthalate) -Terpoly (propoxylated bisphenol A-dodecenyl succinate)-Terpoly (propoxylated bisphenol A-fumarate), mixtures thereof and the like.

Amorphous polyester resins have a number average molecular weight ( _Mn ) of, for example, from about 5,000 to about 100,000, from about 10,000 to about 75,000, or about 5 as measured by gel permeation chromatography (GPC). From about 50,000 to about 50,000. The weight average molecular weight (M _w ) of the amorphous polyester resin is, for example, about 2,000 to about 100,000, about 15,000 to about 85,000, or about 5, as determined by GPC using polystyrene standards. 000 to about 80,000. The broad molecular weight distribution ( _Mw / _Mn ) or polydispersity of the amorphous polyester resin is, for example, from about 2 to about 8, from about 2 to about 6, and from about 3 to about 5.

  The disclosed amorphous polyester resins generally comprise a polycondensation catalyst and a heavy organic catalyst comprising reacting a suitable organic diol with a suitable organic diacid in the presence of an anhydride, eg, dodecyl succinic anhydride (DDSA). It can be prepared by a condensation process. Generally, stoichiometric equimolar ratios of organic diol and organic diacid are utilized, but in some cases the boiling point of the organic diol is, for example, from about 180 ° C. to about 230 ° C. , An excess of diol (eg, ethylene glycol or propylene glycol) by about 0.2-1 molar equivalent may be utilized and removed by distillation during the polycondensation process. The amount of catalyst utilized varies and may be selected in an amount as disclosed herein, and more specifically, for example, from about 0.01 to about 1 mole percent of the amorphous polyester resin, or It may be selected to be in an amount of about 0.1 to about 0.75 mol%.

  Examples of organic diacids or diesters selected for the preparation of amorphous polyester resins are as shown herein: fumaric acid, maleic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid , Azelaic acid, sebacic acid, decanoic acid, 1,2-dodecanoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid And mesaconic acid, diesters or anhydrides thereof. The organic diacid is selected to be, for example, in an amount of about 48 to about 52 mole percent, or about 1 to 10 mole percent of the amorphous polyester resin.

  Examples of diols include aliphatic diols that are utilized for the preparation of the disclosed amorphous polyester resins and may be included in the reaction mixture or added to the reaction mixture. The amorphous polyester may be selected in an amount of about 45 to about 55 mol%, or about 48 to about 52 mol%, contains about 2 to about 36 carbon atoms, and contains 1,2-ethanediol, 1,3 -Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Decanediol, 1,12-dodecanediol, alkylene glycols such as ethylene glycol or propylene glycol, propoxylation Scan phenol A and ethoxylated bisphenol A. The organic diol is selected, for example, to be in an amount of about 48 to about 52 mole percent of the amorphous polyester resin.

  In some embodiments of the present disclosure, one type of amorphous polyester can be prepared from these combinations of monomers of Comparative Examples A and B as illustrated in Table 1 below as a replacement for anhydrous dodecyl The amount of succinic acid (DDSA) monomer is less than about 50% of the sum of the amounts listed, less than about 16%, from about 8 to about 15.9%, from about 8 to about, based on solids. 15%, about 8 to about 13%, about 9 to about 12.8%, or about 9.5 to about 12.8% by weight of the dodecyl succinic anhydride monomer is utilized and the amorphous polyester of Comparative Example A The product is terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate) terpoly- (propoxy). The amorphous polyester product of Comparative Example B is terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (Ethoxylated bisphenol A-terephthalate) terpoly- (ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-trimellitate).

(Bisphenol)
Many bisphenols can be selected for the preparation of the disclosed amorphous polyester resins, examples of which are alkoxyalkylated bisphenols, propoxylated BPA, ethoxylated BPA, 1,1-bis (4-hydroxyphenyl) ) -1-phenyl-ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) butane, bis- (4-hydroxyphenyl) diphenylmethane, 2,2- Bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) -2,2-dichloroethylene, bis (4-hydroxyphenyl) -2,2-dichloroethylene, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3-isopropyl- Enyl) propane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, bis (4-hydroxyphenyl) sulfone, 1,4-bis (2- (4-hydroxyphenyl) -2 -Propyl) benzene, 5,5 '-(1-methylethylidene) -bis [1,1'-(bisphenyl) -2-ol] propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1 , 4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, P-bisphenol A, 1,1-bis (4-hydroxyphenyl) ethane, E-bisphenol A, and mixtures thereof And at least one bisphenol is, for example, 1 to about 5 bisphenols, 2 to about 4 bisphenols, 1 to about 2 bisphenols. A kind of bisphenol.

(Crystalline polyester)
Many crystalline polyesters may be selected for the disclosed toner compositions, including suitable known crystalline polyesters. Specific examples of crystalline polyesters that can be selected for the disclosed toner include poly (1,6-hexylene-1,12-dodecanoate) (name 10: 6), poly (1,2-propylene-diethylene-terephthalate). ), Poly (ethylene-terephthalate), poly (propylene-terephthalate), poly (butylene-terephthalate), poly (pentylene-terephthalate), poly (hexalene-terephthalate), poly (heptylene-terephthalate), poly (octylene-terephthalate) , Poly (ethylene-sebacate), poly (propylene-sebacate) (8: 3), poly (butylene-sebacate) (8: 4), poly (nonylene-sebacate) (8: 9), poly (ethylene-adipate) (4: 2), poly (propylene-adipate) (4: ), Poly (butylene-adipate) (4: 4), poly (pentylene-adipate) (4: 4), poly (hexylene-adipate) (4: 6), poly (heptylene-adipate) (4: 7), Poly (octylene-adipate) (1: 8), poly (ethylene-glutarate) (1: 2), poly (propylene-glutarate) (1: 3), poly (butylene-glutarate) (1: 4), poly ( Pentylene-glutarate) (1: 5), poly (hexalene-glutarate) (1: 6), poly (heptylene-glutarate) (1: 7), poly (octylene-glutarate) (1: 8), poly (ethylene- Pimelate) (3: 2), poly (propylene-pimelate) (3: 3), poly (butylene-pimelate) (3: 4), poly (pentylene-pimelate) ) (3: 5), poly (hexalene-pimelate) (3: 6), poly (heptaden-pimelate) (3: 7), poly (1,2-propylene itaconate), poly (ethylene-succinate) (2 : 2), poly (propylene-succinate) (2: 3), poly (butylene-succinate) (2: 4), poly (pentylene-succinate) (3: 5), poly (hexylene-succinate) (3: 6) ), Poly (octylene-succinate) (3: 8), poly (decylene-decanoate) (8:10), poly (ethylene-decanoate) (8: 2), poly (ethylene dodecanoate) (10: 2), poly (Nonylene-decanoate) (10: 9), copoly (ethylene-fumarate) -copoly (ethylene-sebacate), copoly (ethylene-fumarate) - copoly (ethylene - decanoate), copoly (ethylene - fumarate) - copoly (ethylene - dodecanoate), optionally, and the like and mixtures thereof. A specific crystalline polyester selected for the disclosed toner is CPE 10: 6, poly (1,6-hexylene-1,12-dodecanoate), dodecanedioic acid and 1,6-hexanediol. More specifically, the crystalline polyester is poly (1,6-hexylene-1,12-dodecanoate) of the following repeating formula / structure:

The crystalline resin has a number average molecular weight (M _n ) of, for example, from about 1,000 to about 50,000, or from about 2,000 to about 25,000, as measured by gel permeation chromatography (GPC). May be. The weight average molecular weight (M _w ) of the crystalline polyester resin is, for example, from about 2,000 to about 100,000, or from about 3,000 to about 80,000, as determined by GPC using polystyrene standards. Also good. The molecular weight distribution (M _w / M _n ) of the crystalline polyester resin is, for example, about 2 to about 6, and more specifically about 2 to about 4.

  The disclosed crystalline polyester resin can be prepared by a polycondensation process by reacting a suitable organic diol with a suitable organic diacid in the presence of a polycondensation catalyst. Generally, stoichiometric equimolar ratios of organic diol and organic diacid are utilized, but in some cases, when the boiling point of the organic diol is about 180 ° C. to about 230 ° C., about 0.2 A ˜1 molar equivalent excess of diol (eg, ethylene glycol or propylene glycol) may be utilized and removed by distillation during the polycondensation process. The amount of catalyst utilized may vary and may be selected to be, for example, from about 0.01 to about 1 mole percent, or from about 0.1 to about 0.75 mole percent of the crystalline polyester resin. Good.

  Examples of organic diacids or diesters selected to prepare the crystalline polyester resin are as shown herein, fumaric acid, maleic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, suberin Acid, azelaic acid, sebacic acid, decanoic acid, 1,2-dodecanoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malon Acids and mesaconic acids, their diesters or anhydrides. The organic diacid is selected, for example, to be in an amount of about 48 to about 52 mole percent of the crystalline polyester resin.

  For example, it is selected in an amount of about 1 to about 10 mole percent, or about 3 to about 7 mole percent of crystalline polyester resin that may be included in the reaction mixture or added to the reaction mixture, and about 2 Examples of organic diols including aliphatic diols containing from about 36 carbon atoms are 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, Alkylene glycols such as 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, ethylene glycol or propylene glycol Etc. The organic diol may be selected in various effective amounts, for example, from about 48 to about 52 mole percent of the crystalline polyester resin.

  Examples of suitable polycondensation catalysts utilized for the preparation of amorphous and crystalline polyesters include tetraalkyl titanates, dialkyltin oxides such as dibutyltin oxide, tetraalkyltins such as dibutyltin dilaurate, dialkyltin oxide Hydroxide, for example, butyltin oxide hydroxide, aluminum alkoxide, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, zinc acetate, titanium isopropoxide, butyl stannic acid available as FASCAT® 4100, Or a mixture thereof or a mixture thereof, wherein the catalyst is, for example, from about 0.01 mole% to about 5 moles, based on, for example, the starting diacid or diester used to make the polyester resin. , From about 0.1 to about 0.8 mole%, from about 0.2 to about 0.6 mole percent, or more specifically, it is selected in an amount of from about 0.2 mole%.

For the toner compositions disclosed herein, the amount of amorphous polyester resin may be as indicated herein, such as from about 70 to about 90% by weight, from about 75 to about 85% by weight, Or about 70 to about 80 wt%, and the amount of crystalline polyester is, for example, about 4 to about 15 wt%, about 5 to about 12 wt%, or about 7 to about 10 wt%, The amounts of wax, colorant and toner additive are as disclosed herein.

(wax)
Many suitable waxes may be selected for the toners shown herein, wherein the wax comprises a mixture of amorphous polyester and crystalline polyester in at least one shell and at least one type of mixture. It may be contained in the polyester resin contained in the shell.

  Examples of optional waxes contained in or on the toner include polyolefins such as polypropylene, polyethylene, etc., such as those available from Allied Chemical and Baker Petrolite Corporation; Michaelman Inc. And wax emulsions available from Daniels Products Company; Eastman Chemical Products, Inc. EPOLENE N-15 ™ available from Sanyo Chemical Industries, Ltd .; low weight average molecular weight polypropylene VISCOL 550-P ™ available from Sanyo Chemical Industries, Ltd .; OMNOVA D1509 ™ available from IGI Chemicals as a wax dispersion; And similar materials. Examples of functionalized waxes that can be selected for the disclosed toners include amines, amides, such as Micro Powder Inc. AQUA SUPERSLIP 6550 ™, SUPERSLIP 6530 ™, fluorinated waxes such as Micro Powder Inc. available from POLYFLUO 190 (TM), POLYFLUO 200 (TM), POLYFLUO 523XF (TM), AQUA POLYFLUO 411 (TM), AQUA POLYSILK 19 (TM), POLYSILK 14 (TM) available from: fluorinated amide wax For example, this is also Micro Powder Inc. MICROSPERSION 19 ™ available from; imide, ester, quaternary amine, carboxylic acid or acrylic polymer emulsions such as JONCRYL 74 ™, 89 ™, 130 ™, 537 ™ and 538 ( (Trademark) (all available from SC Johnson Wax), Allied Chemical, Petrolite Corporation, and chlorinated polypropylene and polyethylene available from SC Johnson Wax. Many of these disclosed waxes may optionally be fractionated or distilled to give specific fractions or portions that meet viscosity and / or temperature criteria, for example, the viscosity is about 10,000 cps. Yes, the temperature is about 100 ° C.

  In some embodiments, the wax is, for example, a wax, water, anionic surfactant or polymer-based stabilizer having a particle diameter of about 100 nanometers to about 500 nanometers, or about 100 nanometers to about 300 nanometers. It is in the form of a dispersion comprising an agent, optionally a nonionic surfactant. In some embodiments, the wax is a polyethylene wax particle, such as POLYWAX® 655, or POLYWAX® 725, POLYWAX® 850, POLYWAX® 500 (POLYWAX®). Wax is commercially available from Baker Petrolite), for example, a distilled portion of the commercially available POLYWAX® 655 called X1214, X1240, X1242, X1244, etc., but in the POLYWAX® 655 fraction Includes non-limiting fractionated / distilled wax. Waxes that provide a specific fraction that meets the viscosity / temperature criteria with an upper viscosity limit of about 10,000 cps and an upper temperature limit of about 100 ° C. may be used. These waxes may range in particle diameter from about 100 to about 500 nanometers, but are not limited to these diameters or particle sizes. Examples of other waxes include FT-100 wax available from Shell (SMDA) and FNP0092 available from Nippon Seiro.

  Surfactants used to disperse the wax are anionic surfactants such as NEOGEN RK® available from Daiichi Kogyo Seiyaku or TAYCAPOWER® BN 2060 available from Tayca Corporation, Alternatively, DOWFAX (registered trademark) available from DuPont may be used.

  The amount of toner wax, in some embodiments, is from about 0.1 to about 20 weight percent, from about 0.5 to about 15 weight percent, from about 1 to about 12 weight percent, 1 to about 10%, about 2 to about 8%, about 4 to about 9%, about 1 to about 5%, about 1 to about 4%, or about 1 to about 3% by weight. The cost of the resulting toner is reduced by adding a small amount of wax (eg, about 4.5 to about 9% by weight based on solids) to the toner surface or to both the toner surface and the toner surface. Can do.

(Coloring agent)
Examples of toner colorants include pigments, dyes, mixtures of pigments and dyes, pigment mixtures, dye mixtures and the like. In some embodiments, the colorant comprises carbon black, magnetite, black, cyan, magenta, yellow, red, green, blue, brown, and mixtures thereof.

  The toner colorant may be, for example, an anionic surfactant to provide pigment particles having a volume average particle diameter of, for example, from about 50 nanometers to about 300 nanometers, from about 125 nanometers to about 200 nanometers, Or you may choose from the pigment dispersion of each color of cyan, magenta, yellow, or black in a nonionic surfactant depending on the case. The surfactant used to disperse each colorant may be any number of known ingredients, for example, an anionic surfactant such as NEOGEN RK ™. . Known Ultimizer equipment may be used to provide the colorant dispersion, but a media mill or other known process may be utilized to make the wax dispersion.

  The amount of toner colorant may vary, for example, from about 1 to about 50%, from about 2 to about 40%, from about 2 to about 30%, from 1 to about 25% by weight of the total solids. 1 to about 18 wt%, 1 to about 12 wt%, 1 to about 6 wt%, about 3 to about 10 wt%. When a magnetite pigment is selected for the toner, the amount can be up to about 80% by weight of solids, for example, about 40 to about 80% by weight, based on total solids, or about 50 to about 75% by weight. There may be.

  Specific toner colorants that can be selected include PALIOGEN VIOLET 5100 (trademark) and 5890 (trademark) (BASF), NORMANDY MAGENTA RD-2400 (trademark) (Paul Ulrich), PERMANENT VIOLET VT2645 (trademark) (Paul Ulrich). , HELIOGEN GREEN L8730 (trademark) (BASF), ARGLE GREEN XP-111-S (trademark) (Paul Ulrich), BRILLIAN GREEN TONER GR 0991 (trademark) (Paul Ulrich) 700, LITHLSC RED (TM) (Aldrich), Scarlet for THERMOPLA ST NSD RED (TM) (Aldrich), LITHORU RUBINE TONER (TM) (Paul Ulrich), LITHOL SCARLET 4440 (TM), NBD 3700 (TM) (BASF), BON RED C (TM) (DominIOLA) RED RD-8192 (TM) (Paul Ulrich), ORACET PINK RF (TM) (Ciba Geigy), PALIOGEN RED 3340 (TM) and 3871K (TM) (BASF), LITHOL FAST SCARLET L4300 (TM), (BASF) (EL) BLUE D6840 (TM), D7080 (TM), K7090 (TM), K6910 (TM) and L7020 (trademark) (BASF), SUDAN BLUE OS (trademark) (BASF), NEOPEN BLUE FF4012 (trademark) (BASF), PV FAST BLUE B2G01 (trademark) (American Hoechst), IRGALITE BLUE BCA (trademark) GeB (trademark) (Ciba) , PALIOGEN BLUE 6470 (TM) (BASF), SUDAN II (TM), III (TM) and IV (TM) (Matheson, Coleman, Bell), SUDUAN ORANGE (TM) (Aldrich), SUDAN ORANGE 220 (TM) BASF), PALIOGEN ORANGE 3040 (trademark) (BASF), ORTHO ORANGE OR 2673 (trademark) (Paul) lrich), PALIOGEN YELLOW 152 (trademark) and 1560 (trademark) (BASF), LITOL FAST YELLOW 0991K (trademark) (BASF), PALIOTOL YELLOW 1840 (trademark) (BASF), NOVAPERM YELLOW FHL YELLOW YE 0305 (trademark) (Paul Ulrich), LUMOGEN YELLOW D0790 (trademark) (BASF), SUCO-GELB 1250 (trademark) (BASF), SUCO-YELLOW D1355 (trademark) (BASF), SUCO FASTDEL5 (trademark) , D1355 ™ and D1351 ™ (BASF), HOSTAPERM P INK E (TM) (Hoechst), FANAL PINK D4830 (TM) (BASF), CINQUASIA MAGENTA (TM) (DuPont), PALIOGEN BLACK L9984 (TM) (BASF), PIGMENT BLACK K801 (TM) (carbon) (BASF) REGAL (R) 330 (Cabot), CARBON BLACK 5250 (TM) and 5750 (TM) (Columbian Chemicals), etc., or mixtures thereof.

  Examples of colorants include pigments present in aqueous dispersions, such as those commercially available from Sun Chemical, such as SUNPERSE BHD 6011 ™ (Blue 15 Type), SUNPERSE BHD 9312 ™ (Pigment Blue 15). ), SUNPERSE BHD 6000 (trademark) (Pigment Blue 15: 3 74160), SUNPERSE GHD 9600 (trademark) and GHD 6004 (trademark) (Pigment Green 7 74260), SUNPERSE QHD 6040 (entry) RID (PSP) 9668 (trademark) (Pigment Red 185), SUNSPERSE RHD 9365 (trademark) 9504 (trademark) (Pigment Red 57), SUNSPERSE YHD 6005 (trademark) (Pigment Yellow 83), FLEXIVESE YFD 4249 (trademark) (Pigment Yellow 17) (SUNPERSE YHD 6020 (trademark) and P60g trademark 741). ), SUNSPERSE YHD 600 ™ and 9604 ™ (Pigment Yellow 14), FLEXIVESE LFD 4343 ™ and LFD 9736 ™ (Pigment Black 7), and mixtures thereof. Selectable aqueous colorant dispersions for the toner compositions disclosed herein include those commercially available from Clariant, such as HOSTAFINE Yellow GR ™, HOSTAFINE Black T ™ and Black TS ( (Trademark), HOSTAFINE Blue B2G (TM), HOSTAFINE Rubine F6B (TM) and magenta dry pigments such as Toner Magenta 6BVP2213 and Toner Magenta EO2, which are dispersed in water and / or surfactant. Good.

  Examples of toner pigments selected and available in wet cake or concentrated form containing water can be easily dispersed in water using a homogenizer or ground by ball mill by simply stirring. It can be dispersed by grinding with an attritor or grinding with a media mill. In other cases, the pigments are only available in dry form, so dispersion in water can be atomized using, for example, an M-110 microfluidizer or Ultimateizer, and optionally the ionic surfactants described above. By passing the pigment dispersion about 1 to about 10 times through the chamber of the microfluidizer while adding an optional component such as an agent or nonionic surfactant, or for example, a Branson 700 ultrasonic generator Is pulverized by a ball mill, an attritor, or a media mill.

  Further examples of specific colorants include magnetites such as Mobay magnetite MO8029 ™, MO8960 ™; Columbian magnetite; MAPICO BLACKS ™ and surface treated magnetite; Pfizer magnetite CB4799 ™, CB5300. (Trademark), CB5600 (trademark), MCX6369 (trademark); Bayer magnetite, BAYFERROX 8600 (trademark), 8610 (trademark); Northern Pigments magnetite, NP-604 (trademark), NP-608 (trademark); Magnox magnetite TMB- 100 (TM), TMB-104 (TM) or the like, or a mixture thereof.

  Specific further examples of pigments present in the toner in an amount of 1 to about 40 wt%, 1 to about 20 wt%, or about 3 to about 10 wt% total solids include phthalocyanine HELIOGEN BLUE L6900 (trademark) ), D6840 (TM), D7080 (TM), D7020 (TM), PYLAM OIL BLUE (TM), PYLAM OIL YELLOW (TM), PIGMENT BLUE 1 (TM) (available from Paul Ulrich & Company, Inc.), PIGMENT VIOLET 1 (TM), PIGMENT RED 48 (TM), LEMON CHROME YELLOW DCC 1026 (TM), E.I. D. TOLUIDINE RED (TM) and BON RED C (TM) (available from Dominion Color Corporation, Ltd., Toronto, Ontario), NOVAPERM YELLOW FGL (TM), HOSTAPER PINK E (TM), manufactured by Hoechst. I. CINQUASIA MAGENTA (trademark) available from DuPont de Nemours & Company. Examples of magenta include, for example, 2,9-dimethyl-substituted quinacridone and anthraquinone dyes identified as CI 60710 in Color Index, CI Dispersed Red 15, CI Solvent Red, which is a diazo dye identified as CI 26050 in Color Index. 19 or a mixture thereof. Specific examples of cyan include copper tetra (octadecylsulfonamido) phthalocyanine, x-copper phthalocyanine pigment identified as CI 74160 by Color Index, CI Pigment Blue, Anthracene Blue identified as CI 69810 by Color Index, Special Blue X -2137, etc., or mixtures thereof. Specific examples of yellow that can be selected include diarylide yellow 3,3-dichlorobenzideneacetoacetanilide, a monoazo pigment specified as CI 12700 by Color Index, CI Solvent Yellow 16, and Foron Yellow SE / GLN as Color Index. Specific nitrophenylamine sulfonamides, CI Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,4-dimethoxyacetoacetanilide, Permanent Yellow FGL. Colored magnetite, for example a mixture of MAPICO BLACK ™ and the cyan component, may also be selected as a pigment. The pigment dispersion comprises pigment particles dispersed in an aqueous medium using an anionic dispersant / surfactant or a nonionic dispersant / surfactant, wherein the amount of dispersant / surfactant is about 0.5. To about 10% by weight, or about 1 to about 7% by weight.

(Toner composition)
The toner compositions shown herein include, for example, US Pat. Nos. 5,593,807; 5,290,654; 5,308,734; 5,370,963; 120,967; 7,029,817; 7,736,832, 8,466,254 and may be prepared by emulsion aggregation / fusion methods as described in many patents. it can.

  In some embodiments, the toner composition uses any known emulsion aggregation process, for example, an emulsion comprising one amorphous polyester resin and a crystalline polyester resin, and the optional colorant, optional component, It may be prepared by a process of agglomerating a mixture of wax and optional toner additive, aggregating it, and then fusing the agglomerated mixture. The above resin mixture emulsion is prepared by dissolving a known phase inversion process, for example, an amorphous polyester resin, a crystalline polyester resin, in a suitable solvent and then water containing a stabilizer and optionally a surfactant (for example, degreasing). May be prepared by a process of adding ionic water).

  Examples of suitable optional stabilizers selected for the toner process shown herein include aqueous ammonium hydroxide solutions, water soluble alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, Lithium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, or barium hydroxide; ammonium hydroxide; alkali metal carbonates such as sodium bicarbonate, lithium bicarbonate, potassium bicarbonate, lithium carbonate, potassium carbonate, Examples include sodium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, barium carbonate or cesium carbonate, or mixtures thereof. In some embodiments, a particularly desirable stabilizer is sodium bicarbonate or ammonium hydroxide. Stabilizers are typically present in an amount of, for example, from about 0.1 to about 5%, such as from about 0.5 to about 3% by weight of the colorant, wax and resin mixture. If such a salt is added as a stabilizer, in some embodiments it may be desirable that no incompatible metal salt be present in the composition.

  Suitable dissolving solvents for use in the toner process disclosed herein include alcohols, ketones, esters, ethers, chlorinated solvents, nitrogen containing solvents, and mixtures thereof. Specific examples of suitable solvents include acetone, methyl acetate, methyl ethyl ketone, tetrahydrofuran, cyclohexanone, ethyl acetate, N, N dimethylformamide, dioctyl phthalate, toluene, xylene, benzene, dimethyl sulfoxide, mixtures thereof, and the like. It is done. The resin mixture of amorphous polyester and crystalline polyester may be dissolved in a solvent at a high temperature, for example, about 40 ° C. to about 80 ° C., such as about 50 ° C. to about 70 ° C. or about 60 ° C. to about 65 ° C. The temperature is in some embodiments below the glass transition temperature of the mixture of wax and amorphous polyester. In some embodiments, the resin mixture is heated to the solvent at a temperature that is higher but lower than the boiling point of the solvent (eg, about 2 ° C. to about 15 ° C. or about 5 ° C. to about 10 ° C. below the boiling point of the solvent). Dissolve.

  Optionally, additional stabilizers (eg, surfactants) may be added to the disclosed aqueous emulsion media to further stabilize the resin mixture. Suitable surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants. In some embodiments, the use of anionic and nonionic surfactants may further help stabilize the agglomeration process in the presence of a coagulant.

  Examples of anionic surfactants include sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecyl naphthalene sulfate, dialkylbenzene alkyl, sulfate and sulfonate, abietic acid, an anionic surfactant, NEOGEN® Brand. An example of a suitable anionic surfactant is NEOGEN (registered trademark) RK available from Daiichi Kogyo Seiyaku Co., Ltd. (Japan), or Tayca Corporation (Japan), which consists mainly of sodium dodecylbenzenesulfonate. TAYCAPOWER® BN2060.

Examples of the cationic surfactant include dialkylbenzene alkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkyl benzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C ₁₂ , C ₁₅ , C _17. Trimethylammonium bromide, halide salt of quaternized polyoxyethylalkylamine, dodecylbenzyltriethylammonium chloride, MIRAPOL® and ALKAQUAT® available from Alcaril Chemical Company, SANISOL available from Kao Chemicals ( Registered trademark) (benzalkonium chloride). An example of a suitable cationic surfactant is SANISOL® B-50, available from Kao Corporation, consisting primarily of benzyldimethylalkonium chloride.

  Examples of nonionic surfactants include polyvinyl alcohol, polyacrylic acid, metalloose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether , Polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly (ethyleneoxy) ethanol (from Rhone-Poulenc Inc.) IGEPAL CA-210 (registered trademark), IGEPAL CA-520 ( Registered trademark), IGEPAL CA-720 (registered trademark), IGEPAL CO-890 (registered trademark), IGEPAL CG-720 (registered trademark), IGEPAL CO-290 (registered trademark), ANTAROX 890 (registered trademark) and ANTAROX 897 (registered trademark) Available as a registered trademark). One example of a suitable nonionic surfactant is Rhone-Poulenc Inc., which consists primarily of alkylphenol ethoxylates. ANTAROX® 897 available from

  Accordingly, a mixture of a crystalline polyester resin emulsion and an amorphous polyester resin emulsion using a homogenizer in the presence of a wax containing a colorant and optionally a flocculant (eg, aluminum sulfate), for example, at a pH of about 3 to about 5. Can be mixed and agglomerated. Slowly increase the temperature of the resulting blend to about 40 ° C. to about 65 ° C., or about 35 to about 45 ° C., for example, to agglomerate particles having a diameter of about 2 to about 15 microns, or about 3 to about 5 microns. To obtain this temperature, maintain at this temperature for about 3 hours to about 9 hours (e.g., about 6 hours), after which an amorphous polyester emulsion, and optionally a wax emulsion, may be added to create a shell that is agglomerated. The particle size is increased from about 4 microns to about 7 microns, then a wax emulsion may optionally be used and optionally additional amorphous polyester emulsion for the second shell may be added. The final agglomerated particle mixture may then be neutralized with aqueous sodium hydroxide or buffer solution, for example, to a pH of about 8 to about 9. The agglomerated particles are then heated to about 50 ° C. to about 90 ° C., the particles are fused, and the particle size is about 1 to about 15 microns, for example about 5 to about 7 microns, or about 5 to about 7 microns, FPIA SYSEX analyzer Alternatively, it may be a toner composite having a shape factor of, for example, from about 105 to about 170, from about 110 to about 160, or from about 115 to about 130, as measured by scanning electron microscope (SEM) and image analysis (IA).

  Further, with respect to the emulsification / aggregation / fusion process, after aggregation, the agglomerates are fused as shown herein. The resulting agglomerated mixture may be fused by heating to a temperature about 5 ° C. to about 30 ° C. higher than the Tg of the amorphous resin. Generally, the agglomerated mixture may be heated to a temperature of about 50 ° C to about 95 ° C, or about 75 ° C to about 90 ° C. In some embodiments, the agglomerated mixture may be agitated by an agitator having a blade rotating at about 200 to about 750 revolutions per minute to fuse the particles, for example, for about 3 to about 9 hours. May be.

  Optionally, the particles may be controlled during the fusion by adjusting the pH of the resulting mixture. In general, to control the particle size, for example, a base such as sodium hydroxide may be used and the pH of the mixture may be adjusted to about 5 to about 8.

  After fusing, the mixture may be cooled to room temperature (about 25 ° C.) and the resulting toner particles may be washed with water and then dried. Drying may be performed by any suitable method, including lyophilization, and is typically performed at a temperature of about −80 ° C. for about 72 hours.

After aggregation and fusion, the toner particles, in some embodiments, as determined by a Coulter counter, have an average particle diameter as indicated herein of about 1 to about 15 microns, about 4 to About 15 microns, or about 6 to about 11 microns, such as about 7 microns. The volumetric particle size distribution (GSD _V ) of the toner particles may range from about 1.20 to about 1.35, and in some embodiments, less than about 1.25, as determined by a Coulter counter. .

  Further, in some embodiments of the present disclosure, the pre-toner mixture comprises a colorant, and optionally waxes and other toner components, stabilizers, surfactants, and both the crystalline polyester and the disclosed amorphous polyester. May be prepared by combining them into an emulsion or multiple emulsions. In some embodiments, the pH of the pre-toner mixture may be adjusted to about 2.5 to about 4 with an acid (eg, acetic acid, nitric acid, etc.). Further, in some embodiments, the pre-toner mixture may optionally be homogenized. When homogenizing the pre-toner mixture, homogenization may be performed, for example, by mixing at about 600 to about 4,000 revolutions per minute, for example, using a TKA ULTRA TURRAX T50 probe homogenizer.

  After preparation of the pre-toner mixture, the agglomeration mixture is made by adding a flocculant (coagulant) to the pre-toner mixture. The flocculant is generally composed of an aqueous solution of a divalent cation material or a multivalent cation material. Flocculants are, for example, polyaluminum halides such as polyaluminum chloride (PAC), or the corresponding bromides, fluorides or iodides, polyaluminum silicates such as polyaluminum sulfosilicate (PASS), and aluminum chloride, nitric acid Aluminum, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrate, calcium oxalate, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, It may be a water-soluble metal salt containing magnesium bromide, copper chloride, copper sulfate and combinations thereof. In some embodiments, the flocculant may be added to the pre-toner mixture at a temperature below the glass transition temperature (Tg) of the emulsion containing the amorphous polyester. In certain embodiments, the flocculant may be added in an amount of about 0.05 to about 3 parts per hundred (pph), about 1 to about 10 pph, based on the weight of the toner. The flocculant may be added to the pre-toner mixture over a period of about 0 to about 60 minutes, and agglomeration may be performed with or without maintaining homogenization.

  More specifically, in some embodiments, the toner of the present disclosure makes or prepares a latex emulsion containing (i) a mixture of amorphous polyester resin, crystalline polyester resin, water and surfactant. Making or preparing a colorant dispersion containing a colorant, water and an ionic surfactant, or a nonionic surfactant; (ii) the latex emulsion and the colorant dispersion and optional Blending element additives (eg wax); (iii) to the resulting blend a polyvalent metal ion coagulant, metal ion coagulant, polyvalent metal halide coagulant, metal halide coagulant or any of these Adding a coagulant comprising the mixture; (iv) adding the resulting mixture to the glass transition temperature (Tg) of the amorphous polyester resin. Agglomerate to produce a core by heating to a temperature below; (v) optionally adding further latex composed of an amorphous polyester resin emulsion and optionally a wax emulsion to obtain a shell; (vi) hydroxylation Add sodium solution and raise the pH of the mixture to about 4, then add sequestering agent to partially remove coagulant metal from the agglomerated toner in a controlled manner; (vii) pH of about 7 to about 9 Heating the resulting mixture of (vi) to a temperature above the Tg of the amorphous resin mixture; (viii) maintaining the heating step until fusion or fusing of the resin and colorant begins; (ix) By altering the pH of the mixture of (viii) to a pH of about 6 to about 7.5, Polyester, crystalline polyester, to obtain toner particles comprised of a wax and a colorant; optionally (x), by isolating the toner can be prepared by emulsion / aggregation / fusion.

  In the specific toner emulsification / aggregation / fusion process disclosed above, a coagulant is included over time if desired to assist in controlling particle aggregation and fusion. It may be added to the mixture to be weighed. For example, the flocculant, in one embodiment, over at least about 5 minutes to about 240 minutes, about 5 to about 200 minutes, about 10 to about 100 minutes, about 15 to about 50 minutes, or about 5 to about 30 minutes. , And may be added to the mixture containing the resin while measuring. The flocculant or additive can be added while maintaining the mixture in a stirred state of about 50 rpm (revolutions per minute) to about 1,000 rpm, or about 100 rpm to about 500 rpm. Can be deviated from the above range, and can be performed at a temperature lower than the glass transition temperature of the amorphous polyester resin (for example, about 100 ° C, about 10 ° C to about 50 ° C, or about 35 ° C to about 45 ° C), The temperature may deviate from these ranges.

  The resulting particles may be agglomerated until a predetermined desired particle size is obtained, and the particle size is monitored during the growth process until the desired or predetermined particle size is reached. During the growth process, a composition sample may be removed and analyzed using, for example, a Coulter counter to determine and measure the average particle size. Thus, by maintaining the temperature elevated or, for example, from about 35 ° C. to about 100 ° C. (but the temperature may be outside these ranges), or slowly from about 35 ° C. to about 45 ° C. The resulting mixture is brought to this temperature, for example from about 0.5 hour to about 6 hours, in some embodiments from about 1 hour to about 5 hours (but from these ranges Aggregating particles may be obtained by aggregating the particles by maintaining the time). When the predetermined desired particle size is reached, the growth process is stopped.

  Once the desired final particle size of the toner particles is achieved, a base is used and the pH of the mixture is adjusted to a value of about 6 to about 10, in one embodiment, and about 6.2 to about 7, in another embodiment. However, a pH outside these ranges may be used. Adjustment of the pH may be utilized to freeze (ie, stop) toner particle growth. Bases used to stop toner particle growth include any suitable base (eg, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, etc.). May be. In a specific embodiment, ethylenediaminetetraacetic acid (EDTA) may be added to help adjust the pH to the desired value described above. In specific embodiments, the base may be added in an amount from about 2 to about 25% by weight of the mixture, and in more specific embodiments from about 4 to about 10% by weight of the mixture, but outside these ranges. Different amounts may be used.

  After agglomerating to the desired particle size, the particles may be fused to the desired final shape, for example, by fusing the resulting mixture from about 55 ° C to about 100 ° C, from about 75 ° C to about 75 ° C. Although it may be performed by heating to 90 ° C., about 65 ° C. to about 75 ° C., or any desired or effective temperature of about 75 ° C., temperatures outside these ranges may be used, In order to prevent or minimize plasticization, the temperature may be lower than the melting point of the crystalline resin. For fusing, a temperature higher or lower than the disclosed temperature may be used, which is related to the toner components selected (eg, resins and resin mixtures, waxes and colorants). Note that it is okay.

  The fusing may be carried out and performed for any desired or effective time, for example, about 0.1 hours to about 10 hours, about 0.5 hours to about 8 hours, or about 4 hours or less, Times outside these ranges may be used.

  After fusing, the disclosed mixture may be cooled to room temperature (typically about 20 ° C. to about 25 ° C.) (although temperatures outside this range may be used). If desired, it may be cooled quickly or slowly. A suitable cooling method may include introducing cold water into a jacket around the reactor containing the individual toner components. After cooling, the toner particles may optionally be washed with water and then dried. For example, drying may be performed by any suitable drying method, including lyophilization, having a relatively narrow particle size distribution, and a lower number ratio geometric standard deviation (GSDn) of about 1.15 to about 1.40, about 1 The toner particles may be as narrow as .18 to about 1.25, about 1.20 to about 1.35, or 1.25 to about 1.35.

  Toner particles prepared according to the present disclosure may have, in some embodiments, the volume average diameter disclosed herein (also referred to as “volume average particle size” or “D50v”), Specifically, the volume average diameter may be about 1 to about 25, about 1 to about 15, about 1 to about 10, or about 2 to about 5 microns. D50v, GSDv and GSDn can be determined by using a measuring device such as a Beckman Coulter Multisizer 3 operated according to the manufacturer's instructions. A representative sampling may be performed as follows. A small amount of toner sample (about 1 g) is obtained, filtered through a 25 micrometer sieve, then placed in an isotonic solution to obtain a concentration of about 10%, and this sample is then operated on a Beckman Coulter Multisizer 3 .

  In addition, the toners disclosed herein may have low temperature melting properties, and therefore these toners may be low or very low melting toners. The disclosed low melting point toner exhibits a melting point of about 80 ° C. to about 130 ° C., about 90 ° C. to about 120 ° C., while the disclosed very low melting point toner is about 50 ° C. to about 100 ° C., about 55 ° C. A melting point of ~ 90 ° C.

(Toner additive)
Any suitable surface additive may be selected for the disclosed toner composition. Examples of additives are surface-treated fumed silica, eg TS-530® obtained from Cabosil Corporation, having a particle size of 8 nanometers and surface-treated with hexamethyldisilane; DeGussa / Nippon HMDS-coated NAX50® silica obtained from Aerosil Corporation; DTMS® silica composed of DTMS-coated fumed silica silicon dioxide core L90, obtained from Cabot Corporation; H2050EP® coated with amino-functionalized organopolysiloxane, obtained from Wacker Chemie; metal oxide, eg TiO ₂ , eg 16 nm in particle size MT-3103® available from Tayca Corporation, surface treated with decylsilane; SMT5103® composed of DTMS coated crystalline titanium dioxide core MT500B obtained from Tayca Corporation ); Untreated P-25® obtainable from Degussa Chemicals; alternative metal oxides such as aluminum oxide, and lubricants such as stearates or long chain alcohols such as , UNXLIN 700 (registered trademark), and the like. In general, silica is applied to the toner surface in order to improve toner fluidity, triboelectricity, mixing control, development stability and transfer stability, and increase the toner blocking temperature. TiO ₂ is applied to improve relative humidity (RH) stability, friction control, development stability, and transfer stability.

  The surface additives silicon dioxide and titanium oxide more specifically should have, for example, a primary particle size greater than about 30 nanometers or at least 40 nanometers, where the primary particle size is, for example, transparent Measured by scanning electron microscope (TEM) or calculated from gas absorption or BET surface area measurements (assuming spherical particles), this surface additive has a total toner coverage of, for example, Applied to the toner surface to give a theoretical surface area coverage (SAC) of about 140 to about 200%. Theoretical SAC (hereinafter referred to as SAC) is a standard Coulter counter in which all toner particles are spherical. If the additive particles have a hexagonal close-packed structure and are distributed on the toner surface as primary particles having a diameter equal to the volume average diameter of the toner measured by the above method. It is calculated. Another measure related to the amount and size of the additive is the sum of “SAC × Size” (surface area coverage multiplied by the primary particle size of the additive in nanometers) for each silica and titania particle. And, more specifically, all additives should have a total SAC × Size range of, for example, about 4,500 to about 7,200. The ratio of silica to titania particles is generally from about 50% silica / 50% titania to about 85% silica / 15% titania (on a weight percent basis).

  Calcium stearate and zinc stearate also increase toner lubrication properties, developer conductivity and electrostatic charge, increase toner charge and charge stability by increasing the number of contacts between toner and single particles. It can also be selected as a toner additive to be mainly applied. Examples of stearates are SYNPRO®, Calcium Stearate 392A and SYNPRO®, Calcium Stearate NF Vegetable or Zinc Stearate-L. In some embodiments, the toner comprises, for example, about 0.1 to about 5% titania, about 0.1 to about 8% silica, and optionally about 0.1 to about 4% by weight. Contains calcium stearate or zinc stearate.

(Production of shell)
Optionally, at least one shell of the optional component of amorphous polyester resin and optional wax resin may be applied to the agglomerated toner particles obtained in the form of the core by any desired or effective method. . For example, the shell resin may be in the form of an emulsion comprising the disclosed amorphous polyester, wax and surfactant. The resulting aggregated particles may be combined with the shell resin emulsion so that the shell resin forms a shell on 80% to 100% of the resulting aggregate.

(Developer composition)
A developer composition composed of the toner shown in the present specification and carrier particles is also included in the present disclosure. In some embodiments, the developer composition comprises the disclosed toner particles mixed with carrier particles to make a two-component developer composition. In certain embodiments, the concentration of toner in the developer composition may range from about 1 to about 25%, such as from about 2 to about 15% by weight of the total weight of the developer composition.

  Examples of carrier particles suitable for mixing with the disclosed toner compositions include particles that can electrostatically impart a charge of the opposite polarity to the toner particles, such as granular zircon, granular silicon, Examples include glass, steel, nickel, ferrite, iron ferrite, and silicon dioxide. The selected carrier particles may be used with or without a coating, which is generally a fluoropolymer, such as a polyvinylidene fluoride resin; a styrene terpolymer; methyl methacrylate; a silane, For example, triethoxysilane; tetrafluoroethylene; other known coatings.

  In applications where the described toner is used with an image development device (eg, xerographic imaging system) that uses roll fusing, the carrier core is a polymethyl methacrylate having a weight average molecular weight of 300,000-350,000. It may be at least partially coated with a (PMMA) polymer, such as that available from Soken. PMMA is a polymer having a positive charge that generally imparts a negative charge to the toner upon contact. The coating, in some embodiments, has a coating weight of about 0.1 to about 5%, or about 0.5 to about 2% by weight of the carrier. PMMA may optionally be copolymerized with any desired comonomer so that the resulting copolymer retains the appropriate particle size. Comonomers suitable for copolymerization may include monoalkylamines or dialkylamines such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diisopropylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, and mixtures thereof. Until the polymer coating adheres to the carrier core by mechanical impact and / or electrostatic attraction, the carrier core is about 0.05 to about 10% by weight polymer based on the weight of the coated carrier particles, for example Carrier particles may be prepared by mixing with about 0.05 to about 3% by weight of polymer. Using various effective and appropriate means such as cascade roll mixing, tumbling, grinding, shaking, electrostatic powder cloud spraying, fluidized bed mixing, electrostatic disc treatment, electrostatic curtain treatment, the polymer is applied to the surface of the carrier core. It may be applied. The mixture of carrier core particles and polymer is then heated to melt the polymer and fuse to the carrier core particles. The coated carrier particles are then cooled and then classified to the desired particle size.

  The carrier particles may be mixed with the toner particles in any suitable combination, for example, about 1 to about 5 parts by weight of toner particles are mixed with about 10 to about 300 parts by weight of toner particles.

  The disclosed toner compositions contain known charge additives, such as alkylpyridinium halides, hydrogen sulfate, other known charge control additives, in effective amounts, such as from about 0.1 to about 10% by weight. Or from 1 to about 5% by weight. Surface additives that can be added to the toner composition after washing or drying include, for example, metal salts, metal salts of fatty acids, colloidal silica, metal oxides, mixtures thereof, etc. disclosed herein. The additives are usually present in an amount of about 0.1 to about 2% by weight. See U.S. Pat. Nos. 3,590,000, 3,720,617, 3,655,374, and 3,983,045. Examples of specific suitable additives include zinc stearate and AEROSIL R972® available from Degussa in an amount of about 0.1 to about 2%, which may be added during the agglomeration process. Well, it may be blended into the produced toner product.

  Further, the present disclosure provides for applying the toner composition described herein to a photoconductor, transferring the developed image to a suitable substrate, such as paper, and subjecting the toner composition to heat and pressure. A method is provided for developing a latent xerographic image comprising fusing a toner composition to a substrate by exposing.

  Specific embodiments will now be described in detail. These examples are intended to be illustrative and are not limited to the materials, conditions, or processing parameters shown herein. All parts were percentages by solids weight unless otherwise indicated, and particle size was measured using a Multisizer 3® Coulter Counter available from Beckman Coulter.

  For the following example, coagulation may be measured at various temperatures (51 ° C., 52 ° C., 53 ° C., 54 ° C., 55 ° C.) and then the coagulation value may be plotted against temperature. The temperature at which the coagulation rate becomes 20% is considered as the toner blocking temperature.

  Solidification refers to the percentage of toner that does not flow through the sieve after the prepared toner is maintained in an oven at a specific temperature (eg, 51 ° C.). The temperature may then be increased from 51 ° C. to 52 ° C., then 53 ° C., etc., and the coagulation value can be measured at each of these temperatures. The coagulation value (at each temperature) was then plotted against temperature, and the temperature at which the coagulation value was about 20% was determined to be the blocking temperature.

  More specifically, 20 grams of toner having an average particle size of about 5 to about 8 microns, prepared as shown herein, is added to about 2 to about 4% of surface additives (eg, silica and / or titania). And blended through a 106 micron sieve. Ten grams of each toner sample is placed in a separate aluminum weighing pan and the samples are placed at various temperatures (51 ° C, 52 ° C, 53 ° C, 54 ° C, 55 ° C, 56 ° C, 57 ° C), 50% RH bench. The top environmental chamber was allowed to equilibrate for 24 hours. After 24 hours, the toner sample was taken out and cooled in air for 30 minutes before measurement.

  Each cooled toner sample was transferred from the top weighing pan to a 1,000 micron sieve placed on top of the sieve stack (top (A) 1,000 microns, bottom (B) 106 microns). The difference in weight is measured and the difference gives the weight (m) of toner that has moved to the sieve stack. The sieve stack containing the toner sample was placed in the holder of the Hosokawa flow tester device. The tester was moved for 90 minutes by vibration with an amplitude of 1 millimeter. When the flow test time was over, the weight of the toner remaining on each sieve was measured and the thermal coagulation rate% was calculated using 100 * (A + B) / m. Where A is the mass of toner remaining on the 1,000 micron sieve, B is the mass of toner remaining on the 106 micron sieve, and m is placed on top of a series of stacked sieves. The total mass of toner. The coagulation obtained at each temperature was then plotted against temperature, and the point at which 20% of the coagulation from this plot was interpolated (or extrapolated) corresponded to the blocking temperature.

Example I
Under nitrogen, a 1 liter Buchi reactor was fitted with a mechanical stirrer, bottom drain valve and distillation apparatus, propoxylated bisphenol A (433.8 grams, 53.25 wt%), terephthalic acid (109.4 grams, 23.25%). 4 wt%), dodecenyl succinic anhydride (DDSA) (100.5 grams, 16 wt%), trimellitic anhydride (9.5 grams, 2.33 wt%) and the catalyst FASCAT® 4100, butyl stannic acid ( 2.5 grams), then heated to 230 ° C. over 2-3 hours and maintained at 230 ° C.-235 ° C. for an additional 8 hours. During this time, water was collected in the distillation receiver. The resulting mixture was then heated at 225 ° C. and a vacuum was applied for 6 hours (2-3 millimeters-Hg) followed by an acid number of 4.19 mg / gram KOH, softening point of 101.4 ° C. Obtained. The resulting mixture was then heated at 190 ° C., then fumaric acid (16.7 grams, 3.9 wt%) and hydroquinone (0.5 grams) were added, then heated to 203 ° C. over 3 hours. Thereafter, the reduced pressure state was further applied for 3 hours until the softening point was 120.2 ° C. and the acid value was 14.2 mg / gram KOH. Then terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-fumarate)-(propoxylated bisphenol A- The reaction product of trimellitate was placed in a container and cooled to room temperature (eg, about 25 ° C.).

  An emulsion of amorphous polyester resin prepared as above was prepared by dissolving 100 grams of this resin in 100 grams of methyl ethyl ketone and 3 grams of isopropanol. The resulting mixture was then heated to 40 ° C. with stirring and 5.5 grams of ammonium hydroxide (10% aqueous solution) was added dropwise to the mixture followed by 200 grams of water over 30 minutes. And dripped. Subsequently, the obtained dispersion was heated to 80 ° C., and methyl ethyl ketone was removed by distillation to obtain an aqueous dispersion of an amorphous polyester resin having a solid content of 60.4%. The particles of the amorphous polyester emulsion were measured by an electron microscope to have a particle diameter of 155 nanometers.

(Examples II to IV)
By repeating the process of Example I above using the amount of DDSA shown in Table 2, terpoly- (propoxylated bisphenol A-terephthalate) -terpoly- (propoxylated bisphenol A-dodecenyl succinate) The products of Examples II-IV of) -terpoly- (propoxylated bisphenol A-fumarate)-(propoxylated bisphenol A-trimellitate) were prepared individually.

  Comparative resins A and B are available from Kao Corporation, and comparative resin A is terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate). ) Terpoly- (propoxylated bisphenol A-fumarate), comparative resin B is terpoly- (propoxylated bisphenol A-terephthalate) terpoly- (propoxylated bisphenol A-dodecenyl succinate)- Terpoly- (ethoxylated bisphenol A-terephthalate) terpoly- (ethoxylated bisphenol A-dodecenyl succinate) -terpoly- (propoxylated bisphenol A-trimellitate) -terpoly- (ethoxylated bisphenol A-to It is a mellitate).

In Table 2 for one type of resin properties, Tg is measured by using a TA Instruments Q1000 differential scanning calorimeter under nitrogen flow at a temperature range of 0 ° C. to 150 ° C. and a heating rate of 10 ° C./min. Glass transition temperature. Acid value (AV) is 0.5 grams of resin test material dissolved in THF, 2-3 drops of phenolphthalein is added as an indicator, and 0.1N potassium hydroxide (KOH) in methanol is titrated. Measured by ASTM D 974 method used as an agent. The softening point (Ts) was measured with a Mettler Toledo FP83HT drip apparatus and measured at an initial temperature of 100 ° C. and a heating rate of 10 ° C./min. The resin average volume particle size was measured by a Coulter counter. M _n and M _w are the number average molecular weight and weight average molecular weight in thousands (4.3 equals 4,300), respectively, determined by GPC.

(Example V)
An emulsion containing crystalline resin CPE 10: 9 was prepared as follows.

  An aqueous emulsion of crystalline polyester resin poly (1,9-nonylene-succinate) obtained from DIC Chemicals was prepared by dissolving 100 grams of this resin in ethyl acetate (600 grams). The resulting mixture was then added to 1 liter of water containing 2 grams of sodium bicarbonate and homogenized at 4,000 rpm for 20 minutes, then heated to 80 ° C. to 85 ° C. to distill off the ethyl acetate. The resulting aqueous crystalline polyester emulsion had a solid content of 32.4% by weight and a particle size of 155 nanometers.

Example VI
An emulsion containing crystalline polyester CPE 10: 6 was prepared as follows.

  An aqueous emulsion of crystalline polyester resin poly (1,6-hexylene-succinate) obtained from DIC Chemicals was prepared by dissolving 100 grams of this resin in ethyl acetate (600 grams). The resulting mixture was then added to 1 liter of water containing 2 grams of sodium bicarbonate and homogenized at 4,000 rpm for 20 minutes, then heated to 80 ° C. to 85 ° C. to distill off the ethyl acetate. The resulting aqueous crystalline polyester emulsion had a solid content of 35% by weight and a particle size of 150 nanometers.

(Example VII)
(Preparation of toner using 9% by weight wax)
A 2 liter glass reactor fitted with an overhead mixer, 100 grams of the emulsion containing the amorphous resin of Example I above with a solids content of 60.4 grams, and Example V above with a solids content of 8.64 grams. 25 grams of emulsion containing a crystalline resin emulsion, 36.12 grams of wax-dispersed polypropylene (30.65 wt% solids) obtained as OMNOVA D1509® from IGI Chemicals, 40.21 grams Of cyan pigment PB15: 3 (17.89% by weight) was added. Separately and homogeneously, 2.15 grams of Al ₂ (SO ₄ ) ₃ (27.85 wt%) was added as a flocculant. The resulting mixture was heated to about 40 ° C., and the mixture particles were agglomerated while being stirred at 250 rpm (number of rotations per minute) with a magnetic stirrer. The particle size is monitored with a Coulter counter until the core particles have a volume average particle size of about 4.6 μm (micron), then the above prepared amorphous resin emulsion with a solid content of 33.6 grams is added as a shell material. As a result, core-shell structured particles having an average particle size of about 5.6 microns were obtained. The pH of the resulting agglomerated particles is then raised to 8.5 by adding 4 wt% sodium hydroxide (NaOH) solution, and then 4.62 grams of EDTA (39 wt%) is added to The growth was frozen. After freezing, the reaction mixture is heated to 85 ° C., fused, and the final toner particle size is about 6 microns in average volume diameter and roundness is a Sysmex FPIA 3000 analysis available from Malvern Instruments. If measured by machine, about 0.970 is obtained. The resulting fused particles were then cooled to room temperature (about 25 ° C.), separated by sieving (25 millimeters), filtered, then washed with water and lyophilized to obtain final toner particles. .

(Examples VIII to XIII)
Toners were prepared by repeating the process of Example VII above, except that the amounts and properties of amorphous resin, crystalline resin, DDSA and wax were as quoted in Table 3 below.

(Toner solidification (blocking)
The toner blocking performance results in Table 4 below were determined as disclosed herein, and the control toner was comprised of one amorphous resin (16 wt% DDSA) and crystalline polyester CPE 10: 9. A toner having both the indicated blocking temperature, while containing 16% by weight DDSA resin and the low cost crystalline polyester resin CPE 10: 6 when the wax is 9% and 4.5% by weight. When the crystalline polyester CPE 10: 6, which has a low blocking temperature and is inexpensive, was used, the plasticity of the amorphous resin was too high and / or CPE 10: 6 could not be recrystallized from the amorphous resin. By using a single amorphous resin and reducing the DDSA content (12.8 wt% and 9.5 wt%), a low cost toner containing CPE 10: 6 crystalline resin has improved coagulation ( This shows that plasticization is optimal when the wax is both 9% and 4.5% by weight. For example, an amorphous resin composed of a small amount of DDSA is expected to be cheaper at about 0.20 to 0.25 dollars / kg compared with the cost of the amorphous resin B of the comparative example.

  The toner of Example VII in Table 4 had a good blocking temperature of 53.7 ° C. with an amorphous resin composed of 16% by weight DSA, containing crystalline polyester CPE 10: 9. For the toners of Examples VIII and XI, the blocking temperature was relatively poor at <51.9 ° C. The toners of Examples IX, X, XII, and XIII utilize low cost CPE 10: 6 resin, the amorphous resin is composed of 9.5% or 12.8% DSA, and the blocking temperature is It was very excellent at 52.5 ° C. or higher. These results show, for example, that the cost-effective crystalline polyester CPE 10: 6 resin contains less than 16% by weight of other specified components (eg, wax) and DDSA, eg, 9.5 to 12.8%. The toner containing with% amorphous polyester resin had excellent blocking temperature.

  The fusing properties of the toners in Table 5 below are good cold offsets compared to similar commercially available Xerox 7000 toners that do not contain a component selected from the group consisting of at least one of dodecyl succinic anhydride and dodecyl succinic acid. And exhibiting hot offset, wrinkle MFT and gloss, the amorphous polyester resin comprises from about 8 to about 15.9% by weight of this component or process thereof.

It is considered that the gloss level can be increased by optimizing the amorphous polyester resin M _n / M _w .

Claims (10)

  The amorphous polyester resin is composed of an amorphous polyester resin, a crystalline polyester resin, a colorant and a wax, and the amorphous polyester resin is at least one of carboxylic acid, dicarboxylic acid, benzenetricarboxylic acid, at least one bisphenol, dodecyl succinic anhydride and dodecyl succinic acid. A toner composition made by catalytic polymerization of a monomer of a component selected from the group consisting of wherein the amorphous polyester resin comprises from about 8 to about 15.9% by weight of said component.   The dodecyl succinic anhydride and at least one of the components of the dodecyl succinic acid are present in an amount of about 8 to about 13 weight percent, the carboxylic acid is terephthalic acid, the dicarboxylic acid is fumaric acid, The toner composition according to claim 1, wherein the benzenetricarboxylic acid is trimellitic acid.   The toner composition of claim 1, wherein the dodecyl succinic anhydride and at least one of the components of the dodecyl succinic acid are present in an amount of about 9.5 to about 12.8 wt%.   The carboxylic acid is terephthalic acid, the dicarboxylic acid is fumaric acid, the benzenetricarboxylic acid is trimellitic acid, and the at least one bisphenol is 1,4-bis (2- (4-hydroxyphenyl). ) -2-propyl) benzene P-bisphenol A, 1,1-bis (4-hydroxyphenyl) ethane E-bisphenol A, and mixtures thereof, wherein the dodecyl succinic anhydride is about 9.5 to The toner composition of claim 1, wherein the toner composition is present in an amount of about 12.8 wt%.   The carboxylic acid is terephthalic acid, the dicarboxylic acid is fumaric acid, the crystalline polyester is poly (1,6-hexylene-1,12-dodecanoate), and the component is dodecyl succinic anhydride The toner composition according to claim 1.   An amorphous polyester resin, a crystalline polyester, a core of wax and a colorant, and at least one shell enclosing the core and composed of an amorphous polyester resin, and optionally a wax, for the core and the shell Amorphous polyesters are made by catalytic polymerization of carboxylic acid, dicarboxylic acid, benzenetricarboxylic acid, at least one bisphenol and dodecyl succinic anhydride or dodecyl succinic acid monomer, and the amorphous polyester resin contains zero percent excess of the dodecyl anhydride. Or the amorphous polyester resin comprises a zero percent excess of the dodecyl succinic acid and the amorphous polyester comprises less than 16 wt% of the dodecyl Or containing Haq acid, or the amorphous polyester resin comprises the dodecyl succinic acid of less than 16% by weight, the toner composition.   Amorphous polyester resins are copoly (propoxylated bisphenol A co-fumarate) -copoly (propoxylated bisphenol A co-terephthalate), terpoly (propoxylated bisphenol A codedodecyl succinate) -terpoly (propoxylated bisphenol A) Co-terephthalate) -terpoly- (propoxylated bisphenol A codedodecyl succinate), the crystalline polyester is poly (1,6-hexylene-1,12-dodecanoate), and the colorant is a pigment The amorphous polyester resin comprises from about 8 to about 15 wt% of the dodecyl succinic anhydride, or the amorphous polyester resin comprises from about 8 to about 15 wt% of the dodecyl succinic acid. Toner described in Composition.   The toner has a blocking temperature of about 52 ° C. to about 55 ° C., the crystalline polyester is poly (1,6-hexylene-1,12-dodecanoate, and the toner is subjected to an emulsification / aggregation / fusion process. The toner composition according to claim 6, which is prepared.   The amorphous resin is present in an amount of about 70 to about 80% by weight, the crystalline polyester resin is present in an amount of about 5 to about 12% by weight, and the wax is about 4 to about 9% by weight. Present in an amount, the colorant is present in an amount of from about 3 to about 10% by weight of solids, and the crystalline polyester is poly (1,6-hexylene-1,12-dodecanoate). Item 7. The toner composition according to Item 6.   Mixing amorphous polyester resin, crystalline polyester resin, colorant and wax, amorphous polyester is selected from the group consisting of carboxylic acid, dicarboxylic acid, benzenetricarboxylic acid, at least one bisphenol, dodecyl succinic anhydride and dodecyl succinic acid The amorphous polyester resin comprises from about 8 to about 15.9% by weight of the compound, and agglomerated and fused to produce toner particles. Including the process.